JPH0777787A - Silver halide photographic sensitive material and image forming method using same - Google Patents

Abstract

PURPOSE:To improve demerits due to speed-up of development processing and reduction of a replenishing amount and to ameliorate treatment aptitude after processing, especially, bleachability by incorporating at least one kind of specified compound in one layer on a support. CONSTITUTION:One layer on the support contains at least one kind of compound being liquid at 25 deg.C and represented by the formula in which each of R1 and R2 is, independently, H, nonsubstituted unsaturated alkyl, or nonsubstituted branched alkyl, and both are not H at the same time, and the total carbon number of both is >=18. This silver halide photographic sensitive material has each at least one or more of silver halide emulsion layers different from each other in color sensitivity and containing yellow, magenta, and cyan dye-forming couplers and and the compound of the formula is used for dispersing the coupler, and at least one emulsion layer containing the coupler contains it.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic light-sensitive material, and more particularly to a photographic light-sensitive material having improved image quality and post-processability, and an image forming method thereof.

[0002]

2. Description of the Related Art Today's widespread photography is to disperse a silver halide emulsion in a water-soluble colloid such as gelatin, coat it on a support, and use a cross-linking agent (hardener) to prevent it from flowing out during development processing. It is a cross-linked product. In addition to these, various additives have been used in photographic light-sensitive materials in order to secure various performances. Among these additives, water-insoluble photographic useful reagents {for example, oil-soluble couplers, antioxidants used for preventing fading, color fog or color mixture (for example, alkylhydroquinones, alkylphenols, chromanes, coumarone) Etc.), hardener, oil-soluble filter dye,
Oil-soluble UV absorbers, oil-soluble optical brighteners, DIR compounds (eg, DIR hydroquinones, non-colored DIR couplers), developing agents, dye developers, DDR redox compounds, DDR couplers} are suitable oil-forming agents. Agent, that is, a hydrophilic organic colloid layer (for example, a photosensitive emulsion layer, a filter layer, a back layer, etc.) dissolved in a high boiling point solvent and dispersed in the solution of a hydrophilic colloid, especially gelatin in the presence of a surfactant. Layer, antihalation layer, intermediate layer, protective layer). As the high boiling point organic solvent, a phthalic acid ester compound or a phosphoric acid ester compound is generally used.

The phthalic acid ester compounds and phosphoric acid ester compounds, which are high-boiling organic solvents, disperse the couplers,
Affinity with colloids such as gelatin, stability of color image,
It has been widely used because it is excellent in the influence on the coloring hue, the chemical stability in the light-sensitive material and the availability at low cost. As described above, various requirements are imposed on the high-boiling point organic solvent used for the recent light-sensitive material.

On the other hand, recently, there is a great need for seeing photographs as early as possible and a need for reducing the amount of waste liquid as much as possible. In order to respond to this, rapid development processing and LR (replenishment amount reduction) are required. It is progressing rapidly. However, such speeding up and LR conversion have many adverse effects. For example, if the processing stain becomes large, the stability of the development processing is impaired, the image storability is impaired, the particles are roughened, the coloring hue becomes cloudy, or unnecessary stain occurs with time after the development processing. It's a problem. Resolving these adverse effects has become a major issue for the development of photosensitive materials in recent years.

Further, in recent years, photographic materials have come to be used after being subjected to various processes after development processing. For example, the surface may be matted or textured using a sprayer or a roller with a surface mold, laminated by sandwiching it with a plastic film, adding color using special paints, and various bleaching agents. May be used to reduce color and bleach. It has been found that the suitability of these can vary greatly depending on the design of the photographic material. For example, depending on the type of coloring material, discoloration by matting agent spray or lamination,
There was a problem that the color was difficult to remove with bleach and the paint was difficult to glue. Therefore, the processability of the photographic material after the development processing has also been a major issue for the light-sensitive material.

[0006]

As is clear from what has been described above, the object of the present invention is to prevent adverse effects associated with speeding up of development processing and LR (replenishment amount reduction), in particular, turbidity of coloring hue, It is an object of the present invention to provide a method for improving unnecessary stains which increase with time after development processing, and also to provide a method for improving the processability of a photographic material after the development processing, especially the bleaching property.

[0007]

The object of the present invention is to:
(1) A silver halide photographic light-sensitive material containing at least one compound represented by the following general formula (1) in the form of a liquid at 25 ° C. in at least one layer on a support.

[0008]

[Chemical 2]

Where R₁And R₂Each independently water
Elementary atoms, unsubstituted unsaturated alkyl groups, unsubstituted branched alkyl groups
Represents a kill group. R₁And R₂May be the same or different
But R ₁And R₂Do not become hydrogen atoms at the same time. R
₁And R₂The total sum of carbon atoms is 18 or more. (2) In (1), the silver halide photographic light-sensitive material is
Different color sensitivity, each consisting of one or more layers, on the carrier
Yellow dye forming coupler containing silver halide emulsion
Layer, silver halide emulsion layer containing magenta dye-forming coupler
And cyan dye forming coupler-containing silver halide emulsion layer
And a photographic light-sensitive material represented by the general formula (1)
The compound is used as a medium for dispersing a coupler, and at least 1
Layer containing coupler containing silver halide emulsion layer
More achieved. (3) In (2), the cap dispersed in the high boiling point oil.
Ra's oil PKa 'is 7.0 or more and 13.0 or less
It is achieved by (4) The light-sensitive material of (2) to (3) is mixed in at least one bath.
Development consisting of processing solutions with H of 10.8 or more and 12.5 or less
This is achieved by processing in the processing step. (5) Use the color photographic light-sensitive material of (2) to (3) as the first developer.
Content of bromide compound (black and white developer) is 0.02 or more
Color reversal with 0.1 mol / l or less developer
It is achieved by processing.

The compound represented by the general formula (1) used in the present invention will be described in detail below.

The branched alkyl group in the general formula (1) may be a single component or a mixture of several isomers (hereinafter referred to as a branched mixture), but a branched mixture has a low melting point. preferable. Further, the unsaturated alkyl group in the general formula (1) may be a mixture of cis / trans isomers (hereinafter referred to as an isomer mixture) or a single compound of either cis or trans, but is particularly an isomer mixture. It is preferable that the melting point is low. More specifically, in the general formula (1), R ₁ and R ₂ are hydrogen atoms,
Unsubstituted unsaturated alkyl groups (eg, allyl, oleyl, 10-undecen-1-ol-2-decene-1-)
All), an unsubstituted branched alkyl group (eg, i-propyl, t-butyl, 2-ethylhexyl, 3,5,5-
Trimethylhexyl, i-decyl (branched mixture), i-
Represents dodecyl (branched mixture), 2-hexyldecyl). R ₁ and R ₂ may be the same or different, but R ₁
Neither ₁ nor R ₂ is a hydrogen atom. R ₁ and R ₂
Has a total carbon number of 18 or more, more preferably 20
Or more, and more preferably 24 or more. further,
R ₁ or R ₂ may be an alkyl group having both unsaturation and branching. Specific examples of R ₁ and R ₂ are shown below, but the present invention is not limited thereto.

[0012]

[Chemical 3]

Examples of the compound of the present invention represented by the general formula (1) are shown below, but the present invention is not limited thereto.

[0014]

[Chemical 4]

[0015]

[Chemical 5]

The compound of the present invention can be easily synthesized by a known reaction between phosphorus oxychloride and alcohol. It cannot be said that the reason why these compounds of the present invention are liquid at 25 ° C. has a particularly large effect, but the following three reasons are considered. The faster the development process, the less time is required for the final step of washing with water and the step of rinsing, and the unnecessary components are less likely to be washed out. Furthermore, the content of unnecessary components accumulated in the developer will increase due to the low replenishment rate, but (1) the viscosity of the oil droplets, which are dispersions of the coupler, will decrease, and the developing agent will easily penetrate and the development process will be faster. Become. (2) The low viscosity of oil droplets improves the efficiency of washing out unnecessary components in the water washing process. Therefore, unnecessary components are less likely to remain in the oil droplets. Further, due to the unique effect of the oil of the present invention, the influence of residual unnecessary components (especially the developing agent) (increase in stain with time) is eliminated. (3) In the post-treatment of dye bleaching after the development treatment, the low viscosity of oil droplets accelerates the penetration of the bleaching agent and shortens the bleaching time. In order for the compound of the present invention to be liquid at 25 ° C., it is necessary that R ₁ and R ₂ in the general formula (1) are alkyl groups having a branched or unsaturated bond.

Phosphoric acid esters similar to the compounds of the present invention are already known. For example, regarding trialkyl phosphate, JP-A-54-119235,
No. 54-119921, No. 54-119922 and the like, and a phosphoric acid dialkyl ester which is solid at room temperature is described in European Patent No. 553964A1. Since the trialkyl phosphate ester has physical properties that are significantly different from those of the diester, it has no effect as in the present invention. Also,
The effect of the present invention was not observed for the solid phosphoric acid dialkyl ester for the above reason.

The compound of the present invention is contained in at least one layer on the support, but it may be any hydrophilic colloid layer.
It is preferred to incorporate a dye-forming diffusion-resistant coupler in the silver halide emulsion layer containing at least one dye-forming diffusion-resistant coupler.

The compound represented by the general formula (I) of the present invention mainly functions as a high boiling point organic solvent. Here, the high boiling point means a boiling point of 175 ° C. or higher under normal pressure. The amount of the compound represented by the general formula (I) used can be changed according to the purpose and is not particularly limited. The amount used is preferably 0.0002 g to 10 g, more preferably 0.001 g to ² g, and usually
The weight ratio to a photographically useful reagent such as a coupler is 0.1 to
The range of 4 is general, and the range of 0.1 to 1 is preferable.

The amount of the dispersion comprising the compound represented by the general formula (I) of the present invention and a photographically useful reagent such as a coupler to the dispersion medium is 2 to the dispersion medium 1 in a weight ratio.
0.1, preferably 1.0 to 0.2. Here, as the dispersion medium, for example, gelatin is typical,
Hydrophilic polymers such as polyvinyl alcohol may be mentioned. The dispersion of the present invention may contain various compounds according to the purpose in addition to the compound of the present invention and a photographically useful reagent.

The compound represented by the general formula (I) of the present invention is preferably used in combination with a conventionally known high-boiling point organic solvent. When these well-known high-boiling organic solvents are used in combination, the weight ratio of the compound of the present invention to the total amount of the high-boiling organic solvents is preferably 1% to 90%, more preferably 3% to 50%. use.

Examples of high boiling point solvents which can be used in combination with the compound of the present invention are described in US Pat. No. 2,322,027 and the like. Specific examples of the high boiling point organic solvent having a boiling point of 175 ° C. or higher at normal pressure include phthalic acid esters (eg, diphtyl phthalate, dicyclohexyl phthalate, di-2-
Ethylhexyl phthalate, decyl phthalate, bis (2,4-di-tert-amylphenyl) phthalate, bis (2,4-di-tert-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate),
Esters of phosphoric acid or phosphonic acid (for example, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, The-
2-ethylhexylphenylphosphonate), benzoic acid esters (eg, 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-
Hydroxybenzoate), amides (eg, N, N
-Diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone), sulfonamides (e.g., N-butylbenzenesulfonamide),
Alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (eg, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl) Lactate, trioctyl citrate), aniline derivatives (N, N-dibutyl-2-butoxy-5-tert-octylaniline, etc.),
Hydrocarbons (eg paraffin, dodecylbenzene,
Diisopropylnaphthalene), chlorinated paraffins and the like. Particularly preferred are phosphoric acid esters and phthalic acid esters. As the auxiliary solvent, an organic solvent having a boiling point of 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone. , 2-ethoxyethyl acetate, and dimethylformamide.

Research Disclosure No. 308119 (19) generally describes various techniques and inorganic / organic materials which can be used for the silver halide photographic emulsion of the present invention and the silver halide photographic light-sensitive material using the same.
1989) can be used.

In addition to this, more specifically, for example,
Techniques and inorganic / organic materials that can be used for color photographic light-sensitive materials to which the silver halide photographic emulsion of the present invention can be applied are described in the following parts of EP 436,938A2 and the patents cited below. There is.

Item This section 1) Layer constitution Page 146, line 34 to page 147, line 25 2) Silver halide emulsion Page 147, line 26 to page 148, line 12 3) Yellow coupler No. Page 137, line 35 to page 146, line 33, page 149, line 21 to line 23 4) Magenta coupler, page 149, line 24 to line 28; EP 421,453A1 Page 3, line 5 to page 25, line 55 5) Cyan coupler page 149, line 29 to line 33; European Patent 432,804A2, page 3, line 28 to page 40, line 6) Polymer coupler, page 149, lines 34 to 38; EP 113, line 113, page 39 to page 123, line 37; 7) Colored coupler, page 53, line 42 to page 137, line 34. Page 149, lines 39-45 8) Other functionality Page 7, line 1 to page 53, line 41, page 149, line 46, coupler line to page 150, line 3; EP 435,334 4A2, page 3, line 1 -Page 29, line 50 9) Antiseptic / mildew agent page 150, line 25-line 28 10) Formalin page 149, line 15-17, scavenger 11) Other additives page 153, line 38 ~ Line 47; page 75, line 21 to page 84, line 56, page 27, line 40 to page 37, line 40 of European Patent 421,453A1 12) Dispersion method page 150, line 4 ~ Line 24 13) Support page 150 line 32 to line 34 14) Film thickness and film physical properties page 150 line 35 to line 49 15) Color development step page 150 line 50 to page 151 47th line 16) Desilvering process, page 151, line 48 to page 152, line 53 17) Automatic processor, page 152, 54 Eyes - page 153, line 2 18) washing and stabilizing steps page 153, line 3 to 37 row

The colored coupler used in the light-sensitive material of the present invention is preferably a color coupler having an oil PKa 'of 7.0 or more. Particularly, a color coupler having a size of 8.0 or more is preferable. In the present invention, oil PKa '
Means a value obtained by the following measuring method. That is, 0.15 mmol of coupler (in the case of polymer coupler, polymer coupler containing 0.15 mmol of monomer coupler) was dissolved in 2.4 ml of tri-n-butyl phosphate to give 0.5 g / liter. 9 ml of aqueous potassium chloride solution
Was added, and the mixture was titrated with a 0.5N aqueous potassium hydroxide solution while stirring in a nitrogen stream to adjust the pH at the midpoint of the inflection point to oil PA.
a '. The titrator is Toa Denpa's titrator HTM-1
Type 04 was used.

The present invention can be applied to various silver halide photographic light-sensitive materials. Examples thereof include black-and-white film, black-and-white photographic paper, color negative film, color photographic paper, color reversal film, color reversal photographic paper, color auto positive film, curler auto positive photographic paper and instant film. In particular, a direct-viewing light-sensitive material such as a color reversal film, a color reversal printing paper, a color auto positive film, a curler auto positive printing paper or an instant film is preferable.
Further, it can be preferably used in a color reversal film or a light-sensitive material produced for development processing in a twisting color reversal processing step such as a color reversal printing paper.

The color reversal image forming method specifically forms a positive image as follows. (1) A latent image is formed on the silver halide in the exposed area by image exposure processing. (2) The silver halide in the exposed area is developed by a black and white development process to form a silver image. (3) A latent image is formed on the silver halide remaining in the unexposed area by the reversal process. The reversal treatment includes a light aging treatment and a chemical aging treatment using an aging agent. (4) A color image is formed by color developing unexposed areas of silver halide by color development processing. (5) The silver image is removed by the desilvering process.

More specifically, the color reversal development processing step will be described. Of the color reversal processing steps of the present invention,
The steps from black and white development to color development are as follows. (1) Black-and-white development-water washing-reversal (chemical reversal) -color development (2) Black-and-white development-water washing-light reversal-color development (3) Black-and-white development-water washing-color development Steps (1) to (3) water washing steps Are all US Pat.
The rinsing process described in No. 04,616 can be replaced to simplify the process and reduce waste liquid. Next, the steps after color development will be described. (4) Color development-adjustment-bleach-fixing-washing-stable (5) Color development-washing-bleaching-fixing-washing-stable (6) Color development-adjusting-bleaching-fixing-washing-stable (7) Color development-washing-bleaching-washing-fixing-washing-stable (8) Color development-bleaching-bleach-fixing-washing-stable (9) Color development-bleaching-fixing-washing-stable (10) Color development-bleaching-bleaching Fixing-stability Any one of the steps (1) to (3) and any one of the steps (4) to (10) are connected to form a color reversal processing step. Next, the processing liquid for color reversal processing used in the present invention will be described.

In the present invention, at least one bath in the above development processing step has a pH of 10.8 to 12.5 and a bromide content of 0.005 to 0.1 mol / liter. desirable. Further, the content of bromide in the developing bath is preferably 0.008 or more and 0.05 mol / liter or less, and particularly preferably 0.01 or more and 0.03 mol / liter or less. The bromide is preferably an alkali metal bromide, particularly preferably potassium bromide or sodium bromide. When the pH exceeds 12.5, the stability of the liquid is not preferable.

In the present invention, the bromide content of the black and white developing bath is 0.02 or more and 0.1 or more in the above-mentioned development processing steps.
It is preferable that the developer has a mol / liter or less. Further, it is preferably 0.03 or more and 0.08 mol / liter or less, and particularly preferably 0.03 or more and 0.06 mol / liter or less. The bromide is preferably an alkali metal bromide, particularly preferably potassium bromide or sodium bromide.

Next, the main processing steps of the color image forming method of the present invention will be described in more detail.

[Black-and-White Development Processing] The black-and-white developing solution used in the present invention contains a developing agent. Examples of developing agents include dihydroxybenzenes (eg, hydroquinone, hydroquinone monosulfonate), 3-pyrazolidones (eg, 1-
Phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone), aminophenols (eg, N-methyl-p-aminophenol), ascorbic acid and 1,2,3,4 -A fused heterocyclic compound of a tetrahydroquinoline ring and an indole ring (described in U.S. Pat. No. 4,067,872) can be mentioned. As the developing agent, two or more kinds of compounds may be used in combination. The amount of developing agent used is 1 × per liter of black and white developer.
It is 10 ^{−5 to} 1 mol. In black and white developers, in addition to developing agents, preservatives (eg, sulfite, bisulfite), silver halide solvents, buffers (eg, carbonate, boric acid, borate, alkanolamine), alkaline agents (Eg, hydroxides, carbonates), solubilizing agents (eg, polyethylene glycols, their esters), pH adjusters (eg, organic acids such as acetic acid),
Sensitizer (eg, quaternary ammonium salt), development accelerator (eg,
Thioether compound), surfactant, defoaming agent, hardener,
A viscosity imparting agent, an antifoggant, a swelling inhibitor (eg, sodium sulfate, potassium sulfate), a chelating agent and the like can be added. The sulfite used as the preservative is
Also used as a silver halide solvent. Examples of silver halide solvents other than sulfite include potassium thiocyanate,
Mention may be made of sodium thiocyanate, potassium sulfite, sodium sulfite, potassium disulfite, sodium disulfite, potassium thiosulfate, sodium thiosulfate and 2-methylimidazole. The amount of the silver halide solvent used, as thiocyanate ion, is preferably 0.005 to 0.02 mol, and more preferably 0.01 to 0.015 mol, per liter of the black and white developer. The sulfite ion is preferably used in an amount of 0.05 to 1 mol per liter of black and white developer,
It is more preferable to use 0.1 to 0.5 mol.
Examples of the antifoggant include alkali metal salts of halogen (eg, potassium bromide, sodium bromide, potassium iodide), nitrogen-containing heterocyclic compounds (eg, benzotriazole, 6-nitrobenzimidazole, 5-nitro). Isoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole, hydroxyazaindolizine), mercapto-substituted heterocyclic compound ( (Eg, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole)
And mercapto-substituted aromatic compounds (eg, thiosalicylic acid). Alkali metal salts of bromine are especially preferred. The antifoggant may be added to the photographic material. In that case, the antifoggant is eluted from the photographic material in the black-and-white developing process and accumulated in the black-and-white developing solution. The amount of antifoggant used is 0.00 per 1 liter of black and white developer.
The amount is preferably 1 to 0.1 mol, more preferably 0.01 to 0.05 mol. Examples of the chelating agent include aminopolycarboxylic acid (eg, ethylenediaminetetraacetic acid, hydroxyethyliminodiacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid) and phosphonic acid (eg, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, 1-hydroxyethylidene-1,1
-Diphosphonic acid). As the chelating agent, two or more kinds of compounds may be used in combination. The amount of chelating agent used is 0.1 g to 2 per liter of black and white developer.
It is preferably 0 g, more preferably 0.5 g to 10 g. The pH value of the black and white developer is 8.5.
Is preferably from 1 to 11.5, and from 9.0 to 10.
More preferably, it is 5. The replenishing amount of the black and white developing solution is preferably 50 ml to 500 ml, and more preferably 50 ml to 330 ml per 1 m ² of the photographic material. The processing time of the black and white development step is preferably 20 seconds to 3 minutes, and more preferably 25 seconds to 75 seconds. The treatment temperature is preferably 30 ° C to 50 ° C, more preferably 35 ° C to 45 ° C. In the black and white development process, a water washing process is performed after the black and white development process. In the water washing step, it is preferable to use a multi-stage countercurrent method with two or more tanks in order to reduce the replenishment amount. Replenishment may be reduced to other treatment bath levels (in this case,
Called a rinse bath). The replenishment amount of wash water is 1
It is preferably 3 to 20 liters per m ² . In case of rinse bath, replenishment amount is 50 ml per 1 m ² of photographic material.
To 2 liters, preferably 100 ml to 5
More preferably, it is 00 ml. If necessary, an oxidizing agent, a chelating agent, a buffering agent, a bactericidal agent or the like can be added to the treatment liquid of the rinse bath.

[Reversal Processing] In the color image forming method of the present invention, the reversal processing is performed after the black and white development processing. The reversal process includes a chemical fogging process or a reversal exposure process. The reverse exposure step is preferred. In the case of chemical fogging process, a fogging agent such as tin ion complex salt is used. The reversal process and the color development process may be performed in the same step by adding a fogging agent to the color developing solution described later. In the case of the reversal exposure process, the photographic light-sensitive material is entirely exposed.

[Color Development Processing] The color developing solution is usually an alkaline aqueous solution of an aromatic primary amine type color developing agent. A p-phenylenediamine compound is preferable as the developing agent. Examples of p-phenylenediamine compounds include 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl- Four
-Amino-N-ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and their sulfates, hydrochlorides, phosphates, p-toluenesulfonate,
Mention may be made of tetraphenyl borate and p- (t-octyl) benzene sulfonate. The developing agent is
It is preferable to use 1.0 g to 15 g, and more preferably 3.0 g to 8.0 g, per liter of color developing solution. In addition to developing agents, color developers include buffers (eg, alkali metal carbonates, borates and phosphates), preservatives (eg, hydroxylamine, diethylhydroxylamine, triethanolamine, catechol- 3,5-disulfonate, sulfite, bisulfite), organic solvent (eg, diethylene glycol, triethylene glycol), dye-forming coupler, competitive coupler (eg, citrazinic acid, J acid, H acid), nucleating agent (Eg, sodium boron halide), auxiliary developing agent (eg, 1-phenyl-3-pyrazolidone), viscosity imparting agent, development accelerator, antifoggant, chelating agent and the like can be added. Examples of the antifoggant and the chelating agent are the same as the examples of the additives of the black and white developing solution described above. Examples of the development accelerator include benzyl alcohol, pyridinium compounds (Japanese Patent Publication No. 44-9503, and U.S. Pat. No. 264860).
No. 3171247), cationic dyes (eg, phenosafranine), nitrates (eg, thallium nitrate, potassium nitrate), polyethylene glycol and its derivatives (JP-B-44-9304, and US Pat. No. 2,533,990). No. 2531832, No. 2
No. 57127 and No. 2950970), polythioethers and thioether compounds (described in US Pat. No. 3,012,242). Thioether compounds are particularly preferred. The thioether compound is preferably used in an amount of 0.1 to 10.0 g per liter of the color developing solution. The pH value of the color developing solution is preferably 9 or more, and 9.5 to 1
2.0 is more preferable, and 10.0 to 1
Particularly preferably, it is 1.5. The replenishing amount of the color developing solution is preferably 50 ml to 500 ml, and more preferably 50 ml to 100 ml per 1 m ² of the photographic material. The processing temperature of the color development process is 30 ° C to 50 ° C.
Is preferable, and 31 ° C. to 45 ° C. is more preferable.

[Desilvering Treatment] The desilvering treatment includes an adjusting step, a water washing step, a bleaching step, a fixing step, a bleach-fixing step, a water washing alternative stabilizing step and the like. As a method of replenishing the treatment liquid in each step, the replenisher in each bath can be individually replenished. When the bleach-fixing treatment is carried out after the bleaching treatment, the overflow solution of the bleaching bath may be introduced into the bleach-fixing bath, and the bleach-fixing bath may be supplemented with only the fixing solution.

Bleach used in the bleaching step or the bleach-fixing step
Typical agents are iron (III) aminopolycarboxylate complex salts.
Target. Examples of preferred bleaching agents include ethylenedia
Mintetraacetic acid, ethylenediaminetetraacetic acid dinatri
Um salt, ethylenediaminetetraacetic acid diammonium
Salt, diethylenetriaminepentaacetic acid, cyclohexane
Diamine tetraacetic acid, cyclohexane diamine tetra vinegar
Acid disodium salt, iminodiacetic acid and 1,3-diami
Nopropane tetraacetic acid may be mentioned. Aminopo
The iron (III) complex salt of polycarboxylic acid is composed of iron (III) salt and aminopolyamine.
By adding carboxylic acid to the treatment liquid, the iron (III) complex is added in the treatment liquid.
A salt may be formed. Two or more aminopolycarboxylic acids
You may use together the above. In addition, excess aminopolycarboxylic acid
A surplus (more than forming an iron (III) complex salt) may be used.
In addition to iron (III) complex salts, metals other than iron, such as cobalt and copper
Ionic complex salts may be added to the bleaching solution or the bleach-fixing solution.
Yes. The amount of bleach used per liter of bleaching solution is 0.1
It is preferably from 1 mol to 1 mol, and from 0.2 mol to
More preferably, it is 0.5 mol. PH of bleaching solution
Is preferably 4.0 to 8.0, and 5.0 to
More preferably, it is 6.5. Bleach-fixer 1 liter
The amount of bleach used per tor is 0.05 to 0.5 mol.
The amount is preferably 0.1 mol to 0.3 mol
Is more preferable. The pH of the bleach-fix solution is 5
It is preferably from 8 to 8, and from 6 to 7.5
More preferable. Add a bleaching accelerator to the bleaching bath or bleach-fixing bath.
Alternatively, it can be added to the conditioning bath. Examples of bleach accelerators
Then, a mercapto compound (JP-A-53-141623)
And U.S. Pat. No. 3,893,858 and British Patent
Permission 1138842 each description), disulfide bond
A compound having (see JP-A-53-95630)
Listed), thiazolidine derivative (JP-B-53-9854)
Report), an isothiourea derivative (JP-A-53-9492).
7), thiourea derivative (Japanese Patent Publication No. 45-850).
6 and 49-26586), Thioa
Mido compound (described in JP-A-49-42349), di
Thiocarbamates (Japanese Patent Laid-Open No. 55-26506)
Described) and alkyl mercapto compounds (eg, trithio)
Glycerin, α, α'-thiodipropionic acid, δ-mel
Captobutyric acid). The above alkyl mel
Capto compounds include hydroxyl group, carboxyl group, sulfonic acid
Group, amino group (further alkyl group, acetoxyalkyl
May have a substituent such as a group)
You may stay. The amount of bleaching accelerator used depends on the type of photographic material,
It is determined in consideration of processing temperature and processing time. Mercap
Compound, compound having disulfide bond, thiazol
Using a gin derivative or an isothiourea derivative as a bleaching accelerator
10 per 1 liter of treatment liquid^-FiveThrough 10
^-1It is preferable to use a molar amount of 10^-FourThrough 5 × 10 ^-2
More preferably, it is used in moles. Bleach in bleach
In addition to liquors and bleach accelerators, rehalogenating agents and pH relaxation
Add inorganic acid, organic acid or their salts that have the ability to react
You can Examples of rehalogenating agents include bromide
(Eg, potassium bromide, sodium bromide, ammonium bromide)
) And chlorides (eg potassium chloride, sodium chloride)
And ammonium chloride). loose pH
An example of an acid or salt having an impotence is a nitrate (eg, glass
Sodium acid, ammonium nitrate), boric acid, borax, meta
Sodium borate, acetic acid, sodium acetate, sodium carbonate
, Potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, potassium
Name enoic acid, sodium citrate and tartaric acid
You can

Examples of the fixing agent used in the fixing step or the bleach-fixing step include thiosulfates (eg, sodium thiosulfate, ammonium thiosulfate), thiocyanates (eg, sodium thiocyanate, ammonium thiocyanate, potassium thiocyanate). , Thiourea and thioethers. The amount of the fixing agent used per liter of the bleach-fixing solution is preferably 0.3 mol to 3 mol, more preferably 0.5 mol to 2 mol. The amount of the fixing agent used per 1 liter of the fixer is 0.5
It is preferably from 4 to 4 mol, more preferably from 1 to 3 mol. The pH of the fixing solution is preferably 6 to 10, and more preferably 7 to 9. Known additives such as sulfites, bisulfites, buffers, chelating agents, and sulfinic acids may be added to the fixing solution or the bleach-fixing solution. Further, an ammonium halide (eg, ammonium bromide) or an alkali metal salt of halogen (eg, sodium bromide, sodium iodide) may be added to the fixing solution or the bleach-fixing solution. When the fixing solution or the bleach-fixing solution is diluted with the overflow solution of the bleaching bath, it is preferable that the respective components of the fixing solution or the bleach-fixing solution have relatively high concentrations. Considering the dilution with the overflow liquid, the amount of the discharged liquid can be reduced and the burden of the recovery process can be reduced. The replenishing amount of bleaching solution, fixing solution and bleach-fixing solution is 30 per 1 m ^{2 of} photographic material.
ml to 900 ml is preferred, 50 ml to 15
More preferably 0 ml.

In the desilvering process, finally, a water washing process or a water washing alternative stabilizing process is carried out. If necessary, known additives can be added to the washing water used in the washing step.
Examples of additives include chelating agents (eg, inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid), bactericides, fungicides,
Mention may be made of hardeners and surfactants. The water washing step may use two or more tanks. Further, the washing water may be saved by multi-stage countercurrent washing (for example, 2 to 9 steps). The stabilizing solution used in the washing substitute stabilizing step has a function of stabilizing the dye image. Examples of stabilizing solutions include
Examples thereof include a liquid having a buffering capacity of pH 3 to 6 and a liquid containing an aldehyde (eg, formaldehyde). If necessary, a chelating agent, a bactericidal agent, a fungicide, a hardener, a surfactant and the like can be added to the stabilizing solution. Two or more tanks may be used in the washing and washing stabilizing process. The stabilizing liquid may be saved by multi-stage countercurrent water washing (for example, 2 to 9 stages). A heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, a nitrogen stirring device, an air stirring device, etc. may be provided in the treatment bath of each step as described above, if necessary. . Next, the present invention will be described in detail with reference to Examples.

[0040]

【Example】

Example 1 Preparation of Sample 101 A paper support (thickness 10) laminated on both sides with polyethylene.
(0 micron), the following first to eleventh layers were applied to the front side, and the twelfth to thirteenth layers were applied to the back side to form a color photographic light-sensitive material. The polyethylene coated on the first layer contains titanium oxide (4 g / m ² ) as a white pigment and a trace amount (0.003 g / m ² ) of ultramarine blue as a bluing dye (the chromaticity of the surface of the support is L 88 in the ^* , a ^* and b ^* systems.
It was 0, -0.20, -0.75. ).

(Photosensitive layer composition) The components and coating amount (g /
m ² unit). However, the addition amount of the sensitizing dye is shown in mol per mol of silver. For silver halide, the coating amount in terms of silver is shown. The emulsion used for each layer is Emulsion E described below.
It was made by changing the particle size by changing the temperature according to the manufacturing method of M-1. However, as the emulsion for the 11th layer, a Lippmann emulsion which was not surface-chemically sensitized was used.

First Layer (Antihalation Layer) Black Colloidal Silver ・ ・ ・ 0.10 Color Mixing Inhibitor (Cpd-7) ・ ・ ・ 0.05 Color Mixing Inhibitor Solvent (Solv-4, 5 Equivalents) ・ ・ ・0.12 Gelatin ・ ・ ・ ・ 0.70

Second layer (intermediate layer) Gelatin ... 0.70 Dye (Cpd-32) ... 0.005

Third Layer (Red Sensitive Layer) Silver bromide spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3 equivalents 5.4 × 10 ⁻⁴ ) (average grain size 0.40 μm, grain Size distribution 10%, octahedron) ・ ・ ・ 0.25 gelatin ・ ・ ・ ・ 0.70 Cyan coupler (ExC-1, 2, 3 1: 1: 0.2) ・ ・ ・ ・ 0.30 Anti-fading agent (Cpd-1, 2,3,4,30 each equivalence) ・ ・ ・ 0.18 Anti-staining agent (Cpd-5, 15 equivalence) ・ ・ ・ ・ ・ ・ 0.003 Coupler dispersion medium (Cpd-6) ・ ・ ・ ・ 0.30 Coupler solvent (Solv -1, 3, 5 each equal amount) ... 0.12

4th layer (intermediate layer) Gelatin ... 1.003 Anti-fading agent (Cpd-7) ... 0.08 Anti-mixing agent solvent (Splv-4, 5 equivalents) ... 0.16 Polymer latex (Cpd-8) ... 0.10

Fifth Layer (Green Sensitive Layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-4 2.6 × 10 ⁻⁴ ) (average grain size 0.40 μ, grain size distribution 10%, eight) .. 0.20 gelatin .. .1.00 Magenta coupler (ExM-1, 2 each equivalent) .. .. 0.11 yellow coupler (ExY-1) .. .. 0.03 Anti-fading agent (Cpd-9, 26, 30, 31 are equal amounts ..... 0.15 Anti-staining agent (Cpd-10, 11, 12, 13 in 10: 7: 7: 1 ratio) .... 0.025 Coupler dispersion medium (Cpd- 6) ······························································ 0.15

6th layer (intermediate layer) Same as 4th layer

Seventh Layer (Blue Sensitive Layer) Silver bromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6 each equivalent weight 3.5 × 10 ⁻⁴ ) (average grain size 0.60 μm, grain Size distribution 11%, octahedron) ・ ・ ・ ・ 0.32 Gelatin ・ ・ ・ ・ 0.80 Yellow coupler (ExY-2, 3 equivalents) ・ ・ ・ ・ 0.35 Anti-fading agent (Cpd-14) ・ ・ ・ ・ 0.10 Anti-fading agent (Cpd-30) ... 0.05 Anti-staining agent (Cpd-5,15 in 1: 5 ratio) ... 0.007 Coupler solvent (Solv-2) ... 0.15

Eighth layer (ultraviolet absorber-containing layer) Gelatin ... 0.60 Ultraviolet absorber (equivalent amounts of Cpd-2, 4, 16) ... 0.40 Color mixing inhibitor (Cpd-7, 17 etc.) Amount) ・ ・ ・ 0.03 Dispersion medium (Cpd-6) ・ ・ ・ ・ 0.02 UV absorber solvent (Solv-2, 7 each equivalent amount) ・ ・ ・ ・ 0.08 Irradiation inhibitor (Cpd-18, 19, 20) , 21, 27 in the ratio of 10: 10: 13: 15: 20) ... 0.05

Ninth Layer (Protective Layer) Fine grain silver iodobromide (99 mol% silver bromide, average size 0.05 μ) ... 0.03 Acrylic modified copolymer of polyvinyl alcohol (molecular weight 50,000) ... 0.01 Polymethylmethacrylate particles (average particle size 2.4μ) and silicon oxide (average particle size 5μ) Equivalent ····· 0.05 Gelatin ··· 0.05 Gelatin hardening agent (Equivalent for H-1 and H-2) ) ・ ・ ・ ・ 0.18

10th layer (back layer) gelatin ... 2.50 UV absorber (Equivalent amount for each Cpd-2, 4, 16) ... 0.50 Dye (Equivalent amount for each Cpd-18, 19, 20, 27) ) ... 0.06

Eleventh Layer (Back Layer Protective Layer) Polymethylmethacrylate particles (average particle size 2.4 μ) and silicon oxide (average particle size 5 μ) Equivalent .... 0.05 Gelatin .... 2.00 Gelatin hardener (Equivalent amount of H-1 and H-2) ... 0.14

Preparation of Emulsion EM-1 An aqueous solution of potassium bromide and silver nitrate was simultaneously added to an aqueous gelatin solution at 65 ° C. for 15 minutes with vigorous stirring,
Octahedral silver bromide grains having an average grain size of 0.23 μm were obtained. At this time, 0.3 g of 3,4-dimethyl-1,3 per mol of silver was used.
-Thiazolin-2-thione was added. 1 silver in this emulsion
Chemical sensitization was carried out by sequentially adding 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) per mol and heating at 75 ° C. for 80 minutes. Using the particles thus obtained as a core, the particles are further grown in the same precipitation environment as the first time,
Finally, an octahedral monodisperse core / shell silver bromide emulsion having an average grain size of 0.4 μ was obtained. Coefficient of variation of particle size is about 10%
Met. To this emulsion were added 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mol of silver.
The mixture was heated at 0 ° C. for 60 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion.

ExZK-1 is used as a nucleating agent in each photosensitive layer.
And ExZK-2 are 10 ^-3 for silver halide,
10 ^-2 % by weight, Cpd-22, 28 as a nucleation accelerator,
29 were used at 10 ^-2 wt% each. Further, alkanol XC (Du Pont) and sodium alkylbenzene sulfonate were used as emulsification / dispersion aids in each layer, and succinate and Magefac F-120 (manufactured by Dainippon Ink and Chemicals) were used as coating aids. A stabilizer (equal amounts of Cpd-23, 24 and 25) was used for the content of silver halide and colloidal silver. The total film thickness on the photosensitive layer side was 10.2 μm. This sample was designated as sample number 101. The compounds used in the examples are shown below.

[0055]

[Chemical 6]

[0056]

[Chemical 7]

[0057]

[Chemical 8]

[0058]

[Chemical 9]

[0059]

[Chemical 10]

[0060]

[Chemical 11]

[0061]

[Chemical 12]

[0062]

[Chemical 13]

[0063]

[Chemical 14]

[0064]

[Chemical 15]

[0065]

[Chemical 16]

Solv-1 di (2-ethylhexyl)
Sebacate Solv-2 Trinonyl Phosphate Solv-3 Di (3-methylhexyl) Phthalate Solv-4 Tricresyl Phosphate Solv-5 Dibutyl Phthalate Solv-6 Trioctyl Phosphate Solv-7 Di (2-ethylhexyl) Phthalate

H-1 1,2-bis (vinylfurphonylacetamido) ethane H-2 4,6-dichloro-2-hydroxy 1,3
5-triazine Na salt

ExZK-1 7- (3-ethoxythiocarbonylaminobenzamido) -9-methyl-10-propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate ExZK-2 2- [4- {3- [3- {3- [5-
{3- [2-chloro-5- (1-dodecyloxycarbonylethoxycarbonyl) phenylcarbamoyl] -4
-Hydroxy-1-naphthylthio} tetrazole-1-
Ill] phenyl} ureido] benzenesulfonamide}
Phenyl] -1-formylhydrazine

As shown in Table 1, a part of the coupler dispersion solvent (Solv-2) for the seventh layer (blue-sensitive layer) was changed to the compound of the present invention or the comparative compound for sample 101, and coupler dispersion was performed. Samples 102 to 113 were prepared with the weight of the medium being constant and the other configurations being unchanged.

Samples 101 to 1 prepared as described above
No. 13 was exposed through a black and white separated halftone image. Cyan plate and black and white halftone dot image film were brought into close contact with the sample and exposed to red light (SC-60 filter, Fuji Photo Film Co., Ltd.)
Made). Next, through a magenta plate and a black and white halftone dot image film, green exposure (BPN-53 filter, manufactured by Fuji Photo Film Co., Ltd.) was performed, and then, through a yellow plate and a black and white halftone dot image film. Blue exposure (BPN-
45 and SC-42 filters, manufactured by Fuji Photo Film Co., Ltd. were used. The exposed sample was subjected to the following processing step A to obtain a halftone dot color image.

[Processing Conditions] Processing Step A Time Temperature Temperature Tank Capacity Replenishment Amount Color Development 135 seconds 38 ° C. 28 liters 240 ml / m ² Bleach-fixing 60 seconds 34 ° C. 11 liters 340 ml / m ² Washing with water (1) 40 seconds 32 ℃ 7 liters ----- Washing with water (2) 40 seconds 32 ℃ 7 liters 240 ml / m ² Drying 30 seconds 80 ℃ The auxiliary method of washing water is to supplement the washing bath (2) with the washing bath (2).
The so-called countercurrent method was adopted in which the overflow liquid of (1) was introduced into the washing bath (1). At this time, the carry-out amount of each processing solution by the light-sensitive material was 35 ml / m ² .

The composition of each treatment liquid was as follows. Color developer A Tank solution Replenisher D-Sorbit 0.15 g 0.20 g Sodium naphthalenesulfonate / formalin condensate 0.15 g 0.2 g Nitrilotris (methylenephosphonic acid) penta sodium salt 1.8 g 1.8 g diethylenetriaminepentaacetic acid 0.5 g 0.5 g 1-hydroxyethylidene-1,1-diphosphonic acid 0.15 g 0.15 g diethylene glycol 12.0 ml 16.0 ml benzyl alcohol 14.0 ml 18.5 ml potassium bromide 0. 70 g −− Benzotriazole 0.005 g 0.007 g Sodium sulfite 5.6 g 7.4 g Hydroxylamine / 1/2 sulfate 4.5 g 6.0 g Triethanolamine 6.0 g 8.0 g 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfuric acid ・ 1 / Dihydrate 4.2 g 5.6 g Potassium carbonate 30.0 g 25.0 g Optical brightener (diaminostilbene type) 1.3 g 1.7 g Water is added 1000 ml 1000 ml pH (25 ° C) (KOH or PH adjusted with sulfuric acid) 10.30 10.75

Bleach-fixing solution Tank solution Replenishing solution Ethylenediaminetetraacetic acid ・ 2 sodium ・ dihydrate 4.0 g 4.0 g Ethylenediaminetetraacetic acid ・ Fe (III) ・ Ammonium ・ dihydrate 55.0 g 55.0 g Thio Ammonium sulfate (750 g / l) 168 ml p-toluenesulfinate sodium 30.0 g Ammonium sulfite 35.0 g 3-mercapto-1,2,4-triazole 0.5 g Ammonium sulfate 10.0 g Water was added to 1000 ml pH (25 ° C) ( PH adjustment with ammonia water or acetic acid) 6.20

Rinsing water Tank liquid Both replenishment amount: Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml

The cyan density of the yellow monochromatic coloring area in the halftone dot image area was measured by X-rite to evaluate the degree of yellow turbidity. In addition, the yellow density of the white background is 50
It was measured for 24 hours at -80 ° C RH, and the increase in stain was used to evaluate the increase in stain immediately after the development treatment.
The results are shown in Table 1.

[0076]

[Table 1]

The structural formulas of the compounds cf-59 and cf-62 in the table are shown below. These compounds are compounds which are diphosphates but are not included in the present invention, and are compounds exemplified as compounds 59 and 62 in EP553964A1.

[0078]

[Chemical 17]

As is clear from Table 1, Sample 101 has a high cyan density in the yellow color and is very cloudy. Samples 102-11 using compounds according to the invention
It can be seen that in the case of No. 1, almost no cyan component is generated during yellow color development. On the other hand, Sample 1 using a diphosphate other than the present invention, as shown in EP 553964A1
12 (R ₁ and R ₂ are straight-chain alkyl and solid diphosphate at 25 ° C.) and Sample 113 (R ₁ and R ₂ are aryl diphosphates) have no effect.
Similarly for the increase in stain immediately after the development processing of the white background,
In contrast to Sample 101 and Samples 112 to 113, an increase in concentration is observed, whereas in Samples 102 to 111 of the present invention,
Almost no increase in concentration is seen.

Example 2 Preparation of Sample 201 A sample 201 was prepared by preparing a multilayer color light-sensitive material having the following compositions on a cellulose triacetate film support having a thickness of 127 μ and having an undercoat. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the described use.

First layer: antihalation layer Black colloidal silver 0.3 g Gelatin 2.2 g UV absorber U-1 0.1 g UV absorber U-3 0.05 g UV absorber U-4 0.1 g High boiling point organic solvent Oil-1 0.1 g Microcrystalline solid dispersion of dye E-1 0.1 g

Second layer: intermediate layer Gelatin 0.40 g Compound Cpd-C 5 mg Compound Cpd-J 3 mg Compound Cpd-K 3 mg High boiling organic solvent Oil-3 0.1 g Dye D-4 9 mg

Third layer: intermediate layer Fine grained silver iodobromide emulsion whose surface and inside are fogged (average grain size 0.06 μm, coefficient of variation 18%, AgI content 1 mol%) silver amount 0.05 g gelatin 0.4 g

Fourth Layer: Low Sensitivity Red Sensitive Emulsion Layer Emulsion A Silver amount 0.5 g Emulsion B Silver amount 0.3 g Gelatin 0.8 g Coupler C-1 0.1 g Coupler C-2 0.25 g Coupler C-3 0.1 g Compound Cpd-C 5 mg Compound Cpd-J 5 mg High boiling point organic solvent Oil-2 0.1 g Additive P-1 0.1 g

Fifth layer: Medium-speed red-sensitive emulsion layer Emulsion B Silver amount 0.2 g Emulsion C Silver amount 0.3 g Gelatin 0.8 g Coupler C-1 0.05 g Coupler C-2 0.15 g Coupler C -3 0.2 g High boiling point organic solvent Oil-2 0.1 g Additive P-1 0.1 g

Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.4 g Gelatin 1.1 g Coupler C-1 0.05 g Coupler C-2 0.15 g Coupler C-3 0.1 g Coupler C -9 0.05 g Additive P-1 0.1 g

Seventh Layer: Intermediate Layer Gelatin 0.6 g Additive M-1 0.3 g Color mixing inhibitor Cpd-I 0.03 g Dye D-5 0.02 g Compound Cpd-J 5 mg High boiling point organic solvent Oil- 1 0.02 g

Eighth layer: intermediate layer Silver iodobromide emulsion with fogged surface and inside (average grain size 0.06 μm, variation coefficient 16%, AgI content 0.3 mol%) silver amount 0.02 g gelatin 1 0.0 g Additive P-1 0.2 g Color mixing inhibitor Cpd-A 0.1 g Compound Cpd-C 0.1 g

Ninth layer: low-sensitivity green-sensitive emulsion layer Emulsion E Silver amount 0.5 g Emulsion F Silver amount 0.4 g Gelatin 0.5 g Coupler C-4 0.05 g Coupler C-11 0.15 g Coupler C -7 0.15 g Coupler C-8 0.05 g Compound Cpd-B 0.03 g Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.04 g Compound Cpd-J 10 mg Compound Cpd-L 0 0.02 g High boiling organic solvent Oil-1 0.15 g High boiling organic solvent Oil-2 0.15 g

Layer 10: Medium-speed green-sensitive emulsion layer Emulsion G Silver amount 0.3 g Emulsion H Silver amount 0.2 g Gelatin 0.6 g Coupler C-4 0.05 g Coupler C-11 0.15 g Coupler C -7 0.15 g Coupler C-8 0.05 g Compound Cpd-B 0.03 g Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.05 g Compound Cpd-L 0.05 g High boiling point organic Solvent Oil-1 0.15 g High boiling point organic solvent Oil-2 0.15 g

Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion I Silver amount 0.3 g Emulsion J Silver amount 0.2 g Gelatin 1.0 g Coupler C-4 0.05 g Coupler C-11 0.17 g Coupler C -7 0.17 g Coupler C-8 0.05 g Compound Cpd-B 0.03 g Compound Cpd-E 0.02 g Compound Cpd-F 0.04 g Compound Cpd-K 5 mg Compound Cpd-L 0.02 g High boiling point organic solvent Oil -1 0.17 g High boiling point organic solvent Oil-2 0.17 g

Twelfth layer: intermediate layer Gelatin 0.6 g Compound Cpd-L 0.05 g High boiling point organic solvent Oil-1 0.05 g

Thirteenth layer: Yellow filter layer Yellow colloidal silver Silver amount 0.07 g Gelatin 1.1 g Color mixture inhibitor Cpd-A 0.01 g Compound Cpd-L 0.01 g High boiling point organic solvent Oil-1 0.01 g Dye E-2 microcrystalline solid dispersion 0.05 g

Fourteenth layer: Intermediate layer Gelatin 0.6 g

Fifteenth layer: low-sensitivity blue-sensitive emulsion layer Emulsion K Silver amount 0.4 g Emulsion L Silver amount 0.4 g Gelatin 0.8 g Coupler C-5 0.3 g Coupler C-6 0.1 g Coupler C-10 0.1 g

Sixteenth layer: Medium sensitivity blue-sensitive emulsion layer Emulsion M Silver amount 0.2 g Emulsion N Silver amount 0.3 g Gelatin 0.9 g Coupler C-5 0.4 g Coupler C-6 0.05 g Coupler C-10 0.15g

Seventeenth layer: High-sensitivity blue-sensitive emulsion layer Emulsion O Silver amount 0.4 g Gelatin 1.2 g Coupler C-5 0.1 g Coupler C-6 0.1 g Coupler C-10 0.6 g High boiling organic solvent Oil-2 0.1 g

Eighteenth layer: First protective layer Gelatin 0.7 g UV absorber U-1 0.2 g UV absorber U-2 0.05 g UV absorber U-5 0.3 g Formalin scavenger Cpd-H 0.4 g Dye D-1 0.15 g Dye D-2 0.05 g Dye D-3 0.1 g

19th layer: 2nd protective layer Colloidal silver Silver amount 0.1 mg Fine grain silver iodobromide emulsion (average grain size 0.06 μm, AgI content 1 mol%) Silver amount 0.1 g Gelatin 0.4 g

20th layer: Third protective layer Gelatin 0.4 g Polymethylmethacrylate (average particle size 1.5 μm) 0.1 g Copolymer of methylmethacrylate and acrylic acid 4: 6 (average particle size 1. 5 μm) 0.1 g Silicone oil 0.03 g Surfactant W-1 3.0 mg Surfactant W-2 0.03 g

In addition to the above composition, additives F-1 to F-8 were added to all emulsion layers. Furthermore, in each layer,
In addition to the above composition, a gelatin hardening agent H-1 and coating and emulsifying surfactants W-3, W-4, W-5 and W-6 were added. Furthermore, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, and p-benzoic acid butyl ester were added as antiseptic / antifungal agents.

[0102]

[Table 2]

[0103]

[Table 3]

[0104]

[Table 4]

[0105]

[Chemical 18]

[0106]

[Chemical 19]

[0107]

[Chemical 20]

[0108]

[Chemical 21]

[0109]

[Chemical formula 22]

[0110]

[Chemical formula 23]

[0111]

[Chemical formula 24]

[0112]

[Chemical 25]

[0113]

[Chemical formula 26]

[0114]

[Chemical 27]

[0115]

[Chemical 28]

[0116]

[Chemical 29]

[0117]

[Chemical 30]

With respect to the sample 201, the high boiling point organic solvents Oil-1 and Oil-2 in the 9th, 10th and 11th layers were evenly reduced to give compounds of the present invention or comparative compounds as shown in Table 5. Samples 202 to 209 were created by replacing a certain amount. In Table 5, comparative compounds cf-59 and cf-6
1 is shown below.

[0119]

[Table 5]

[0120]

[Chemical 31]

An image obtained by subjecting each of Samples 201 to 209 thus prepared to a halogen lamp having a color temperature of 3200 ° K as a light source was subjected to a wedge exposure using an optical wedge, and then processed by the development processing method described later to obtain R, G, and For each B color, the three color densities are calculated using the status A4 filter, and R, G,
A characteristic curve of each color B was obtained. In addition, a 4 inch × 5 inch sheet film was prepared, and after uniformly exposed to gray, the film was similarly developed and evaluated for processing unevenness.

The processing steps and processing liquid formulations used will be described. Processing time Time Temperature Tank capacity Replenishment amount 6 minutes 38 ° C 12 liters 2200 ml / m ² First washing 2 minutes 38 ° C 4 liters 7500 ml / m ² Inversion 2 minutes 38 ° C 4 liters 1100 ml / m ² Color development Development 6 minutes 38 ° C 12 liters 2200 ml / m ² before bleaching 2 minutes 38 ° C 4 liters 1100 ml / m ² bleaching 6 minutes 38 ° C 12 liters 220 ml / m ² fixing 4 minutes 38 ° C 8 liters 1100 ml / m 2 ² Second washing 4 minutes 38 ° C 8 liters 7500 ml / m ² Final rinse 1 minute 38 ° C 2 liters 1100 ml / m ²

The composition of each processing liquid was as follows. [First developer] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid / 5 sodium salt 1.5 g 1.5 g Diethylenetriamine pentaacetic acid / 5 sodium salt 2.0 g 2.0 g Sodium sulfite 30 g 30 g Hydroquinone potassium monosulfonate 20 g 20 g Potassium carbonate 15 g 20 g Sodium bicarbonate 12 g 15 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g 2.0 g Potassium bromide 2.5 g 1.4 g Potassium thiocyanate 1.2 g 1.2 g potassium iodide 2.0 mg-diethylene glycol 13 g 15 g Water was added to 1000 ml 1000 ml pH 9.60 9.60 The pH was adjusted with sulfuric acid or potassium hydroxide.

[Reversal Solution] [Tank Solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 3.0 g 3.0 g Stannous chloride dihydrate 1.0 g p-aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water was added to 1000 ml pH 6.00 pH was adjusted with acetic acid or sodium hydroxide.

[Color developer] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 2.0 g 2.0 g Sodium sulfite 7.0 g 7.0 g Trisodium phosphate dodecahydrate 36 g 36 g Potassium bromide 1.0 g-Potassium iodide 90 mg-Sodium hydroxide 3.0 g 3.0 g Citrazine acid 1.5 g 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4- Aminoaniline / 3/2 sulfuric acid monohydrate 11 g 11 g 3,6-dithiaoctane-1,8-diol 1.0 g 1.0 g pH 11.8 12.00 pH was adjusted with hydrochloric acid or sodium hydroxide. [Fixer] Ammonium thiosulfate 80 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water was added to 1000 ml pH 6.60 The pH was adjusted with hydrochloric acid or aqueous ammonia. [Stabilizer] Formalin (37%) 5.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.5 ml Water added 1000 ml

As the developing machine, a suspending machine using a pawl hanger as a developing frame, Model H4R-240 manufactured by Noritsu Koki Co., Ltd. was used.

The results of the experiment are shown in Table 6. Here, the unevenness of the development process is caused by the liquid dripping from the hanger with a nail that is generally used in the hanging machine, and appears as uneven color in the gray color-developed portion. ○ means no occurrence, △ means slight occurrence,
X indicates a case where obvious occurrence, XX indicates occurrence of strength, and XXX indicates a case where extremely strong occurrence is observed. Since unevenness in the development process impairs the image, it is desirable that the degree of occurrence is slight. For the post-bleaching processing of the developed sample, a magenta selective bleaching solution (SR-32: manufactured by Eastman Kodak Company) was prepared according to a standard formulation. The film processed at room temperature was immersed in the bleaching solution, and the time (second) until the density of the original image having a magenta density of 2.0 was reduced by 10% was defined as the bleaching speed. The higher the bleaching speed, the better the workability. However, if it is too fast, the concentration cannot be strictly controlled, and therefore, practically, about 100 seconds is preferable. As can be seen from Table 6, the compounds of the present invention reduce development processing unevenness. On the other hand, a sample using cf-59 (straight chain alkyl having a total number of carbon atoms of 16) or cf-61 (alkyl having an unsaturated bond, but having a total carbon number of 6) which is a known compound described in EP553964A1. No reduction in processing unevenness was observed in 208 and 209. Similarly, for the SR-32 bleach rate, the compounds of the present invention also showed a large accelerating effect, while the comparative compound showed only a slight effect. As for the amount of the compound of the present invention to be used, the effect was particularly large when it was used in an amount of about 5% to 50% based on the total amount of the high boiling point organic solvent.

[0128]

[Table 6]

Example 3 Samples 201 to 209 prepared in Example 2 were tested in the same manner as in Example 2 except that the color developer formulation in the processing solution process of Example 2 was replaced with the following.

[Color developer] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid-5-sodium salt 0.5 g 0.5 g 3,6-dithiaoctane-1,8-diol 0.25 g 0.25 g Sodium sulfite 2.5 g 3.0 g Diethylenetriamine pentaacetic acid / 5 sodium salt 2.0 g 2.0 g Potassium bromide 0.5 g-Potassium iodide 30 mg-Hydroxylamine sulfate 1.5 g 1.8 g N-ethyl-N- (β-methanesulfonamide Ethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 11.0 g 11.0 g pH 10.6 10.8 (pH was adjusted with sodium hydroxide)

When the processing unevenness was evaluated by the same method as in Example 2, none of the samples 201 to 209 was generated. Therefore, the effect of the present invention is, as in the color developing solution of Example 2, during the development process, having a pH of 10.8 or more and a bromide compound concentration of 0.005 mol / liter or more (potassium bromide 0.6
It was found that the effect is large by processing in the development processing step having a processing solution of g / liter or more).

Example 4 Samples 201 to 209 prepared in Example 2 were processed by replacing the first developing solution in the processing step shown in Example 2 with the solution shown below and conducting the same experiment. The results are shown in Table 7.

First developer Mother liquor Replenisher Nitrilo-N, N, N-trimethylenephosphonic acid / 5 sodium salt 3.0 g 3.0 g Diethylenetriamine 5 acetic acid / 5 sodium salt 3.0 g 3.0 g Potassium sulfite 30.0 g 30.0 g Hydroquinone monosulfone Potassium acid salt 27.0 g 33.0 g Potassium carbonate 33.0 g 33.0 g 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.7 g 2.0 g Potassium bromide 5.2 g-potassium thiocyanate 1.2 g 1.3 g Potassium iodide 0.015 g -Water was added and the pH was adjusted with 1000 ml 1000 ml pH (25 ° C) (KOH / sulfuric acid). 9.70 9.85 Photosensitive material 1 using mother liquor and replenisher prepared as above
A running process was performed with a replenishment amount of 500 ml per m ² until the total replenishment amount was three times the capacity of the black and white developing tank. After running, the potassium bromide concentration is 5.5 g / liter, the potassium iodide concentration is 0.014 g / liter, and the pH is
Was 9.80.

[0134]

[Table 7]

The replenishment amount of the first developing solution in Example 4 is 500 ml.
In / m ^2, which is about 1/5 of 2200 ml / m ² of Example 2. A large reduction in the replenishment amount is preferable because it reduces the amount of waste liquid, but as shown in Table 7, there are problems such as strong unevenness in development processing and unnecessary stain increase over time after processing. It could not be put to practical use (Sample 201 in Table 7). It is understood that the use of the compound of the present invention can greatly reduce these processing irregularities and unnecessary stains.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location G03C 7/407

Claims (5)

[Claims] 1. At least one layer on a support has the following general formula:
It is represented by (1) and exists as a liquid at 25 ° C.
Ha containing at least one compound
Silver halide photo-sensitive material. [Chemical 1]Where R₁And R₂Are each independently a hydrogen atom,
Of substituted unsaturated alkyl groups and unsubstituted branched alkyl groups
You R₁And R₂May be the same or different, but R ₁And R
₂Do not become hydrogen atoms at the same time. R₁And R₂Charcoal
The total sum of elementary atoms is 18 or more. 2. A silver halide emulsion layer containing a yellow dye-forming coupler and a magenta dye-forming coupler-containing silver halide emulsion layer each having one or more layers each having different color sensitivities on a support. A color photographic light-sensitive material having an emulsion layer and a silver halide emulsion layer containing a cyan dye forming coupler, wherein the compound represented by the general formula (1) is used as a medium for dispersing a coupler, and at least 1
The silver halide photographic light-sensitive material according to claim 1, which is contained in a coupler-containing silver halide emulsion layer of the layer. 3. The silver halide photographic light-sensitive material according to claim 2, wherein the coupler oil PKa 'dispersed in the high boiling point oil is 7.0 or more and 13.0 or less. 4. At least one bath has a pH of 10.8 or higher 1
4. The treatment according to claim 2 or 3, wherein the treatment is carried out in a developing treatment step constituted by a treatment liquid having a bromide compound content of 2.5 or less and a content of 0.005 or more and 0.1 mol / liter or less. The silver halide photographic light-sensitive material as described in any of the above. 5. The silver halide photographic light-sensitive material according to claim 2, wherein the content of the bromide compound in the first developer (black and white developer) is 0.02 or more and 0.1 mol / liter. An image forming method characterized by performing color reversal processing using the following developing solution.